CN107814873A - A kind of polymer for having surface active function and its preparation method and application - Google Patents
A kind of polymer for having surface active function and its preparation method and application Download PDFInfo
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- CN107814873A CN107814873A CN201610816649.XA CN201610816649A CN107814873A CN 107814873 A CN107814873 A CN 107814873A CN 201610816649 A CN201610816649 A CN 201610816649A CN 107814873 A CN107814873 A CN 107814873A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The present invention relates to polymer arts, disclose a kind of polymer for having surface active function and its preparation method and application, the polymer contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (1), the construction unit B is the construction unit with structure shown in formula (2), and the construction unit C is the construction unit with structure shown in formula (3).The polymer of tool surface active function provided by the invention has good surface-active, viscous water media capabilities and temperature-resistant anti-salt ability concurrently.
Description
Technical field
The present invention relates to polymer arts, in particular it relates to which a kind of polymer for having surface active function, the tool surface are lived
The preparation method of the polymer of sexual function, the polymer for the tool surface active function being prepared by this method, and the tool
Application of the polymer of surface active function as oil displacement agent.
Background technology
In tertiary oil recovery technology, to solve the problems, such as the heatproof of Polymer Used For Oil Displacement, anti-salt property difference, researcher
Propose and introduce function monomer in the molecule and improve the method for polymer molecular weight to improve the apparent viscous of aqueous solutions of polymers
Degree and temperature-resistant anti-salt performance, thus have developed hydrophobic associated polymer, comb polymer, Heat Resistant and Salt Tolerant Polymer etc., but this
Compound of birdsing of the same feather flock together does not have surface-active and washing oil ability.
Ternary combined chemical flooding technology can realize profit ultralow interfacial tension, while keep injected fluid viscosity, greatly
Amplitude improves recovery ratio.But absorption, diffusion and the migration of the mixture of different component chemical agents in reservoir of porous medium etc.
Performance characteristic differs greatly, and causes " chromatographic fractionation effect " during the displacement of reservoir oil in reservoir pore.Surfactant is in displacement simultaneously
During waste increase, recovery ratio and economic benefit reduce.When using highly basic auxiliary agent in addition, all too many levels productions during extraction
Raw serious scale, difficulty is brought to production management.Ensure oil displacement system under high salinity and higher temperature conditions simultaneously
With sufficiently high viscosity and ultralow interfacial tension, it is necessary to break through the frame for utilizing polymer/surfactant compound system in the past
Frame.With reference to the surface-active of high molecular tackifying ability and low-molecular-weight surfactant, introduced on macromolecular chain with excellent
The functional group of surface-active, reaches the effect for not only viscosifying but also reducing interfacial tension, and a kind of material plays polymer and table simultaneously
The effect of two kinds of materials of face activating agent, therefore such macromolecule oil-displacing agent with surface-active will solve to polymerize to a certain extent
Thing-chromatographic fractionation effect problem existing for surfactant combination flooding, simultaneously because the increasing with surface active function polymer
Sticky energy, it also has the function that stable foam, may act as foam stabilizer in foam flooding and polynary foam composite flooding, these are excellent
More performance makes it be had broad application prospects in tertiary oil recovery.
Survey data in recent years shows that low-permeability oil deposit has turned into the key areas of China's In Oil Field Exploration And Development, cut-off
In the end of the year 2008, accumulative 28,700,000,000 tons of the verified oil oil in place in the whole nation, wherein hyposmosis petroleum-in-place is 14,100,000,000 tons, is accounted for
49.2%.Raising with degree of prospecting and the continuous growth to petroleum resources demand, no matter from residual petroleum resource, still open
Send out trend analysis, low-permeability oil deposit by be China's future In Oil Field Exploration And Development main object.It is polymerize in low-permeability oil deposit
When thing drives mining site design, it is necessary to the matching relationship of prior Study Polymer Melts relative molecular mass and reservoir permeability.In Ju Qu areas
When block relative molecular mass is preferred, on the one hand to consider to select Polymer Molecular Weight as high as possible, so as to obtain more
Good polymer displacement of reservoir oil performance, on the other hand will consider matching relationship of the polymer molecule from different permeability oil reservoirs, as far as possible
Increase the enterable oil reservoir interstitial space of polymer solution, polymer flooding control extent is improved, so as to obtain more preferable polymer flooding effect.Section
Polymer flooding, Polymer Molecular Weight can be carried out by grinding worker and obtaining low permeability pay by indoor moveable experimental study
There is certain relation in the matching between low permeability pay permeability, if shouted with polymer molecule radius of gyration with hole
Relation reflects that then matching relationship can be expressed as matching relationship between road radius：For low-permeability oil reservoir, when pore constriction half
When the ratio between footpath and polymer molecule radius of gyration are more than 5 times, injection low relative molecular mass polymer will not block, and be less than
Blocking occurs at 5 times, obtained with major oil reservoir similar in result.If circled round with permeability square root and polymer molecule
The comparison experimental result of radius is stated, and can be expressed as the ratio between permeability square root and polymer molecule radius of gyration and is more than
Oil reservoir will not be blocked when 1.5.Accordingly, it is considered to deposited to the matching between Polymer Molecular Weight and low permeability pay permeability
In certain relation, the polymer of certain molecular weight scope should be synthesized to meet the matching with low-permeability oil deposit.
People deepen continuously to the research for having the polymer of surface active function, develop new kind and new synthetic method
And the focus of current research.But it is inadequate due to recognizing relation between structure and property, it is related to the macromolecular of physicochemical properties
Water solution system again it is extremely complex, up to the present have this field of the polymer of surface active function progress it is slow,
Research for the polymer of the tool surface active function of middle and low permeable reservoir does not almost have.Therefore its structure and performance are studied
Relation, synthesize certain molecular weight scope the copolymer with high surface, there is important theory and application value.
Alkyl or APES acrylate are respectively adopted in US4138381, US4463151 and EP426864
Surface active monomer is copolymerized with acrylamide monomers, the mainly association using the hydrophobic grouping of surface active monomer in water
Effect, so that the viscosity of copolymer increases substantially, the copolymer containing surface active monomer component has more preferable salt tolerant
Property, but amphipathic polymeric monomer component is difficult in bipolymer to interface aggregates, therefore, synthesized copolymer surface-active
It is bad.
In CN1178802A, acrylamide monomers, surface-active macromonomers and ionic comonomer are copolymerized to obtain ternary
Copolymer, the copolymer viscosity is higher but surface-active is poor.Sun Lili of Southwest Petroleum Institute et al. uses homogeneous polymerization process,
A kind of novel high polymer surfactant (PS1) is synthesized, the high molecular surfactant is acrylamide, acrylic acid, methyl
Methyl acrylate terpolymer, the high molecular surfactant reduce the ability of surface tension not as good as low molecular weight surfactant activity
Agent, it is compounded with inorganic salts, due to cooperative effect, can produce the compound property better than single surfactant, makes surface
Power is even lower, but the temperature-resistant anti-salt performance of the high molecular surfactant is poor.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences
Jin Yong et al. has synthesized a kind of non-iron polymerizable with double bond and gathered using toluene di-isocyanate(TDI) and polyethers as primary raw material
Urethane high molecular surfactant, the high molecular surfactant can drop solution surface tension when concentration is 0.06mol/L
To 37.6mN/m (25 DEG C), while good surface-active can be still kept under very low concentrations, in addition, this it is polymerizable it is non-from
The ability that subtype polyurethane high molecule surfactant reduces surface tension increases with the increase of hydrophobic segment proportion,
But the polymerization activity of the non-iron polymerizable polyurethane high molecular surfactant is poor, while heat resistance is poor.
The content of the invention
The invention aims to overcome, current Polymer Used For Oil Displacement can not have good surface-active concurrently, viscous water is situated between
The shortcomings that mass-energy power and temperature-resistant anti-salt ability, while consider the matching from different permeability oil reservoirs, there is provided live on one kind tool surface
Polymer of sexual function and its preparation method and application.
Therefore, the invention provides a kind of polymer for having surface active function, the polymer of the tool surface active function
Containing construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the knot with structure shown in formula (1)
Structure unit, construction unit B are the construction unit with structure shown in formula (2), and construction unit C is with structure shown in formula (3)
Construction unit；Wherein, on the basis of the weight of the polymer of the tool surface active function, construction unit A content is 45-89
Weight %, construction unit B content are that 10-40 weight %, construction unit C content are 1-15 weight %, have surface-active work(
The viscosity average molecular weigh of the polymer of energy is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, R4And R5It is each independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, R7For C1-C17Alkane
Base.
Present invention also offers a kind of method for the polymer for preparing above-mentioned tool surface active function, this method, which is included in, draws
Send out agent and as the water of solvent in the presence of, make monomer D, monomer E and monomer F progress solution polymerization, wherein, the monomer
D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), the monomer F be with
The monomer of structure shown in formula (6)；Wherein, tied in the polymer that the monomer D, monomer E and monomer F dosage to be prepared
Structure unit A content is that 45-89 weight %, construction unit B content are that 10-40 weight %, construction unit C content is 1-15
Weight %, and the viscosity average molecular weigh for the polymer for be prepared is 5,000,000-2,000 ten thousand；The construction unit A be with
The construction unit of structure shown in formula (1), the construction unit B are the construction unit with structure shown in formula (2), the structure list
First C is the construction unit with structure shown in formula (3),
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, R4And R5It is each independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, R7For C1-C17Alkane
Base.
Present invention also offers the polymer of the tool surface active function prepared by the above method.
Present invention also offers application of the polymer of above-mentioned tool surface active function in oil displacement agent.
It is provided by the invention tool surface active function polymer have concurrently good surface-active, viscous water media capabilities and
Temperature-resistant anti-salt ability.
The present invention is lived from the angle of MOLECULE DESIGN by introducing surface active monomer F to provide the surface of polymer
Property, active carbon-carbon double bond makes it have very high reactivity in molecular structure, easily with other various vinyl monomer copolymerizations
Different functional polymers is generated, contains strong anionic property and hydrophilic functional group carboxylic acid group and chain hydrophobic in molecular structure
Group, there is good surface-active.Heretofore described polymer is a kind of controllable acrylamide tool of adjustable molecular weight
The polymer of surface active function, the matching from different permeability oil reservoirs can be met, in combination with high molecular tackifying
With the surface-active of low-molecular-weight surfactant, there is fluidity control and reduce the effect of oil/water interfacial tension, certain
Solves the problems such as chromatographic fractionation effect existing for polymer-surfactant combination flooding in degree, in addition, also efficiently solving
The problem of existing oil displacement system temperature-resistant anti-salt performance difference, therefore such polymer oil-displacing agent is applied to high, medium and low infiltration oil
The nontraditional reservoirs such as Tibetan, high-temperature oil reservoir, high temperature and high salt oil deposit, further it can improve oil recovery factor in tertiary oil recovery.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the solution of polymer P 2, the solution of polymer P 6, the solution of polymer P 8 and the comparative sample KYP solution of the present invention
Apparent viscosity variation with temperature curve map.
Fig. 2 is the solution of polymer P 2, the solution of polymer P 6, the solution of polymer P 8 and the comparative sample KYP solution of the present invention
Surface tension with concentration change curve.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of polymer for having surface active function, and the polymer of the tool surface active function contains structure
Unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (1), institute
It is the construction unit with structure shown in formula (2) to state construction unit B, and the construction unit C is the knot with structure shown in formula (3)
Structure unit；Wherein, on the basis of the weight of the polymer of the tool surface active function, the content of the construction unit A can be with
For 45-89 weight %, preferably 50-75 weight %；The content of the construction unit B can be 10-40 weight %, be preferably
15-40 weight %；The content of the construction unit C can be 1-15 weight %, preferably 5-10 weight %；Live on the tool surface
The viscosity average molecular weigh of the polymer of sexual function can be 5,000,000-2,000 ten thousand, preferably 6,000,000-1,850 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, preferably methylene, R4
And R5It is each independently H or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, it is excellent
Elect C as7-C15Alkyl, more preferably C7-C11Alkyl, R7For C1-C17Alkyl, preferably C7-C15Alkyl, more preferably
For C7-C11Alkyl.
According to the present invention, the C1-C4Alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, just
Butyl, sec-butyl, isobutyl group and the tert-butyl group.
According to the present invention, the C1-C14Alkylidene can be straight or branched, the C1-C14Alkylidene can be with
Including but not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene and sub- uncle
Butyl, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, sub- n-nonyl,
Sub- positive decyl, sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl, preferably methylene.
The alkylidene refers to that alkane loses the residue after two hydrogen atoms, and described two hydrogen atoms can be same carbon
Two hydrogen atoms on atom, two hydrogen atoms that can also be on different carbon atoms can be straight chain or side chain
, for example, the ethylidene can be-CH2CH2- or-CH (CH3)-。
According to the present invention, the C1-C17Alkyl can be straight or branched, the C1-C17Alkyl can include
But it is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle
Amyl group, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl, positive tritriacontyl, just
Tetradecyl, positive pentadecyl, positive palmityl and positive heptadecyl..
According to the present invention, the intrinsic viscosity η of the polymer of the tool surface active function can be 1100-3300mL/g；
The polymer of the tool surface active function is dissolved in and is configured to concentration in the salt solution that salinity is 10000mg/L and is
During 1500mg/L solution, the surface tension of the solution can be 33-38mN/m.Under preferable case, the tool surface-active work(
The intrinsic viscosity η of the polymer of energy is 1250-3050mL/g；The polymer of the tool surface active function is dissolved in salinity
During to be configured to the solution that concentration is 1500mg/L in 10000mg/L salt solution, the surface tension of the solution is 33-35.5mN/
m。
In the present invention, intrinsic viscosity is carried out according to polyacrylamide Intrinsic Viscosity Measurements method as defined in GB12005.1-89
Measure, 10 weight % NaCl solution is determined at 25 DEG C with Ubbelohde viscometer.Surface tension uses Dataphysics
DCAT21 surface tension instruments are measured.Salinity herein refers to Na in simulated formation water+、K+、Ca2+、Mg2+、Cl-、
SO4 2-、CO3 2-Deng the summation of inorganic ion content.
The present inventor has found under study for action, is made up of specific construction unit A, construction unit B and construction unit C
Polymer be used to that during oil displacement agent preferable oil displacement efficiency can be obtained.For example, the construction unit A can be for formula (7) institute
Show the construction unit of structure, the construction unit B can be the construction unit with structure shown in formula (8), the construction unit C
Can be with structure shown in the construction unit of structure shown in the construction unit of structure shown in formula (9), formula (10) and formula (11)
At least one of construction unit,
The present invention also provides a kind of method for the polymer for preparing above-mentioned tool surface active function, and this method includes：Drawing
Send out agent and as the water of solvent in the presence of, make monomer D, monomer E and monomer F progress solution polymerization, wherein, the monomer
D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), the monomer F be with
The monomer of structure shown in formula (6), wherein, tied in the polymer that the monomer D, monomer E and monomer F dosage to be prepared
Structure unit A content is that 45-89 weight %, construction unit B content are that 10-40 weight %, construction unit C content is 1-15
Weight %, and the viscosity average molecular weigh for the polymer for be prepared is 5,000,000-2,000 ten thousand；The construction unit A be with
The construction unit of structure shown in formula (1), the construction unit B are the construction unit with structure shown in formula (2), the structure list
First C is the construction unit with structure shown in formula (3),
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, preferably methylene, R4
And R5It is each independently H or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, it is excellent
Elect C as7-C15Alkyl, more preferably C7-C11Alkyl, R7For C1-C17Alkyl, preferably C7-C15Alkyl, more preferably
For C7-C11Alkyl.
, according to the invention it is preferred to the monomer D, monomer E and monomer F dosage cause structure in the polymer that is prepared
Unit A content be 50-75 weight %, construction unit B content be 15-40 weight %, construction unit C content be 5-10 weight
Measure %.
According to the present invention, the reaction condition of the polymerisation in solution causes the viscous equal molecule of the polymer of gained after polymerisation
Amount can be 5,000,000-2,000 ten thousand, preferably 6,000,000-1,850 ten thousand.
In the present invention, it is necessary to which explanation, the one body approximation are fully converted to the poly- of the tool surface active function
The corresponding construction unit that compound contains, the dosage of the monomer contain corresponding to the polymer of the tool surface active function
Construction unit content it is consistent.
According to the present invention, the dosage of the monomer can in wider range changing, on the basis of the total amount of the monomer,
The dosage of the monomer D can be 45-89 weight %, preferably 50-75 weight %.
According to the present invention, the dosage of the monomer can in wider range changing, on the basis of the total amount of the monomer,
The dosage of the monomer E can be 10-40 weight %, preferably 15-40 weight %.
According to the present invention, the dosage of the monomer can in wider range changing, on the basis of the total amount of the monomer,
The dosage of the monomer F can be 1-15 weight %, preferably 5-10 weight %..
In the present invention, the construction unit of structure shown in the formula (1), the construction unit of structure shown in formula (2), formula (3)
The list of the monomer of structure shown in the construction unit of shown structure, formula (4), the monomer of structure shown in formula (5) and structure shown in formula (6)
The related definition and substance classes of substituent in body are identical with the correspondence noted earlier of the present invention, and the present invention is no longer superfluous herein
State, those skilled in the art should not be construed as the limitation to technical scheme.
The present inventor has found under study for action, is obtained when being reacted by specific monomer D, monomer E and monomer F
Polymer is used to that during oil displacement agent preferable oil displacement efficiency can be obtained.For example, the monomer D can be with knot formula (12) Suo Shi
The structures alone of structure, shown monomer E can be the structures alone with structure shown in formula (13), shown monomer F can be with
The monomer of structure shown in formula (14), with the monomer of structure shown in formula (15) and with the monomer of structure shown in formula (16) extremely
Few one kind,
The method according to the invention, there is no particular limitation for the monomer D, the monomer E and the monomer F total amount,
Can be changed in wider scope, using the water as solvent and the monomer D, the monomer E and the monomer F total amount as
Benchmark, the monomer D, the monomer E and the monomer F total content can be 10-40 weight %, preferably 20-30 weights
Measure %.The method according to the invention, the condition of the solution polymerization can be the conventional condition in this area, such as described poly-
Reaction is closed to carry out in the presence of an inert gas.
Under preferable case, in the present invention, the solution polymerization condition can include：Carry out under adiabatic conditions,
Polymerization time is 2-15 hours, preferably 5-10 hours, more preferably 8-10 hours.
In order to save the energy and reduce cost, the polymerisation is preferably carried out under adiabatic conditions.The inert gas
For the gas not reacted with raw material and product, such as it can be zero group in this area conventional nitrogen or the periodic table of elements
At least one of elemental gas, preferably nitrogen and/or argon gas.
The method according to the invention, the polymerisation are 6-10, more preferably 7-9 preferably in pH value, further preferably
To be carried out under conditions of 7.8-8.5.The pH value can be obtained by adding pH adjusting agent into polymerization system, the pH regulations
Agent can be the conventional various pH adjusting agents in this area, for example, can be in sodium hydroxide, sodium carbonate, potassium carbonate and ammoniacal liquor extremely
Few one kind, preferably sodium hydroxide.
The method according to the invention, there is no particular limitation for the dosage of the initiator, can become in wider scope
Dynamic, on the basis of the monomer D, the monomer E and the monomer F total amount, the dosage of the initiator is 0.01-0.1 weights
Measure %.
The method according to the invention, the initiator can be the conventional various initiators in this area, such as can be choosing
From any two kinds in radical polymerization initiator：The radical polymerization initiator includes azo-initiator, peroxide
Class initiator and redox type initiators.The azo-initiator is selected from azo-bis-iso-dimethyl, the isobutyl of azo two
Amidine hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, the hexamethylene of azo two
Base formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and azo two are different
At least one of heptonitrile；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate,
At least one of benzoyl peroxide and the benzoyl peroxide tert-butyl ester；The redox type initiators be selected from sulfate-
At least one of sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
The method according to the invention, adding chelating agent can prevent metal ion from being had an impact to polymerisation, therefore, excellent
In the case of choosing, the polymerisation is carried out in the presence of chelating agent.The chelating agent can be disodium ethylene diamine tetraacetate, ammonia
Base triacetic acid or ammonium citrate, preferably disodium ethylene diamine tetraacetate.The present invention is not special to the dosage of the chelating agent
Limit, can be changed in wider scope, it is described on the basis of the monomer D, the monomer E and the monomer F total amount
The dosage of chelating agent can be 0.1-0.3 weight %.
The method according to the invention, the dissolubility of polymer can be improved by adding auxiliary agent, it is therefore preferable that in the case of, it is described
Polymerisation is carried out in the presence of auxiliary agent.The auxiliary agent can be at least one of urea, thiocarbamide and ammoniacal liquor, preferably urinate
Element.There is no particular limitation for dosage of the present invention to the auxiliary agent, can be changed in wider scope, with the monomer D, institute
On the basis of the total amount for stating monomer E and the monomer F, the dosage of the auxiliary agent can be 0.01-0.1 weight %.
The method according to the invention, the polymer of different molecular weight can be synthesized by adding molecular weight regulator, it is therefore preferable that
In the case of, the polymerisation is carried out in the presence of molecular weight regulator.The molecular weight regulator can be isopropanol, ammonia
Water, N, N '-at least one of methylene-bisacrylamide and dimethyl sulfourea.The dosage of the molecular weight regulator can root
Selected according to the conventional amount used of this area.For example, on the basis of the monomer D, the monomer E and the monomer F total amount,
The dosage of the molecular weight regulator can be 0.001-0.1 weight %.
Present invention also offers the polymer of the tool surface active function prepared by the above method.
Present invention also offers application of the polymer of above-mentioned tool surface active function as polymer oil-displacing agent, specifically
The technology that application process is well known to those skilled in the art.The polymer of the tool surface active function of the present invention can be used
Make polymer oil-displacing agent, can be suitably used for middle and low permeable reservoir and high-temperature oil reservoir and high temperature and high salt oil deposit, enter in tertiary oil recovery
One step improves oil recovery factor.
The present invention will be described in detail by way of examples below.It is it should be appreciated that described herein specific real
The mode of applying is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In following examples, the method for testing being related to is as follows：
The dissolution time of polymer method as defined in GB12005.8-89 is measured.
The intrinsic viscosity η of polymer polyacrylamide Intrinsic Viscosity Measurements methods as defined in GB12005.1-89 are surveyed
It is fixed, 10 weight %NaCl solution are determined at 25 DEG C with Ubbelohde viscometer.
Viscosity molecular weight is according to formula M=([η]/K)1/αIt is calculated, wherein K=4.75 × 10-3, α=0.80.
The apparent viscosity of polymer solution is tested with Brookfield DV-III viscosimeters, rotating speed 6rmin-1。
Surface tension is determined using Dataphysics DCAT21 surface tension instruments, and test temperature is 30 DEG C.
In following examples, the method for testing for having the apparent viscosity conservation rate of the surface-active polymer aqueous solution includes：Will
Polymer is dissolved in salinity 10000mg/L salt solution that (salinity is in simulated formation water using 1500mg/L concentration
Na+、K+、Ca2+、Mg2+、Cl-、SO4 2-、CO3 2-Deng the summation of inorganic ion content), solution deoxygenation to oxygen content is less than 1mg/
L, by the obtained aqueous solution at 90 DEG C after aging 1 month, 25 DEG C of the above-mentioned aqueous solution are determined with Brookfield viscosimeters
Apparent viscosity, apparent viscosity conservation rate is calculated with below equation：
Used reagent is commercially available chemically pure reagent in following examples, the polymer samples used in comparative example
For KYP.Wherein, KYP is containing acrylamide construction unit and 2- methyl -2- acrylamides for what oil field provided with sample, KYP
Base propane sulfonic acid construction unit, on the basis of KYP weight, the content of acrylamide construction unit is 75 weight %, 2- methyl -2-
The content of acryamidopropanesulfonic acid construction unit is that 25 weight %, KYP viscosity average molecular weigh is 10,100,000, and intrinsic viscosity is
1915mL/g。
Embodiment 1
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 6.00g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone DTE-1 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 37.5g propylene
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acid amides, 19.0g, it is single on the basis of the total content of monomer and distilled water
The total content of body is 25 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 25mg is added to help
Agent urea, 75mg disodium ethylene diamine tetraacetates, 1mL ammoniacal liquor and 10mg isopropanols, while with sodium hydroxide regulation system pH value extremely
7.8, reactor is placed in water-bath, is passed through high pure nitrogen 30 minutes that volumetric concentration is 99.99% to remove polymerisation bottle
In oxygen.Then 20mg ammonium persulfates, 10mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes, it is adiabatic
Reaction 10 hours, obtain the transparent polymer product with viscosity, through be granulated, dry, crush, sieve obtain tool surface-active work(
The polymer P 1 of energy.
According to the dosage of structures alone DTE-1 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (14)
It can calculate and learn, in the polymer P 1 of tool surface active function, the content of the construction unit of derived from acrylamides is about
60 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 30.4 weight %, is derived from
The content of structures alone DTE-1 construction unit shown in formula (14) is about 9.6 weight %.
The intrinsic viscosity for having the polymer P 1 of surface active function is 1252mL/g, and viscosity average molecular weigh is 606 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 33.4mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 18.1mPa.s, and the apparent viscosity at 85 DEG C is 9.3mPa.s, and polymer solution is at 90 DEG C
Under apparent viscosity conservation rate is 90.6% after aging 1 month in substantially free of environment, show obtained tool surface active function
Polymer there is good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 2
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 5.75g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone DTE-2 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 37.0g propylene
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acid amides, 19.75g, on the basis of the total content of monomer and distilled water,
The total content of monomer is 24 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 25mg is added
Auxiliary agent urea, 75mg disodium ethylene diamine tetraacetates, 1mL ammoniacal liquor, while with sodium hydroxide regulation system pH value to 7.8, will react
Device is placed in water-bath, is passed through high pure nitrogen 30 minutes that volumetric concentration is 99.99% to remove the oxygen in polymerisation bottle.So
After sequentially add 10mg ammonium persulfates, 10mg sodium hydrogensulfites, continue to be passed through high pure nitrogen 10 minutes, adiabatic reaction 10 hours,
Obtain the transparent polymer product with viscosity, through be granulated, dry, crush, sieve obtain have surface active function polymer
P2。
According to the dosage of structures alone DTE-2 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (15)
It can calculate and learn, in the polymer P 2 of tool surface active function, the content of the construction unit of derived from acrylamides is about
59.2 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 31.6 weight %, derivative
Content from structures alone DTE-2 construction unit shown in formula (15) is about 9.2 weight %.
The intrinsic viscosity for having the polymer P 2 of surface active function is 1558mL/g, and viscosity average molecular weigh is 802 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 33.8mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 23.8mPa.s, and the apparent viscosity at 85 DEG C is 13.3mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 92.3% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 3
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 4.25g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(16) structures alone DTE-3 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 40.0g propylene
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acid amides, 18.25g, on the basis of the total content of monomer and distilled water,
The total content of monomer is 26 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 50mg is added
Auxiliary agent urea, 100mg disodium ethylene diamine tetraacetates, 1mL ammoniacal liquor and 5mgN, N- methylene-bisacrylamide, while use hydroxide
Reactor is placed in water-bath to 8.0 by sodium regulation system pH value, is passed through the high pure nitrogen 30 minutes that volumetric concentration is 99.99%
To remove the oxygen in polymerisation bottle.Then 15mg ammonium persulfates, 10mg sodium hydrogensulfites are sequentially added, continues to be passed through high-purity
Nitrogen 10 minutes, adiabatic reaction 8 hours, the transparent polymer product with viscosity is obtained, through being granulated, drying, crushing, sieving
To the polymer P 3 of tool surface active function.
According to the dosage of structures alone DTE-3 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (16)
It can calculate and learn, in the polymer P 3 of tool surface active function, the content of the construction unit of derived from acrylamides is about
64 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 29.2 weight %, is derived from
The content of structures alone DTE-3 construction unit shown in formula (16) is about 6.8 weight %.
The intrinsic viscosity for having the polymer P 3 of surface active function is 1856mL/g, and viscosity average molecular weigh is 998 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 34.3mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 27.1mPa.s, and the apparent viscosity at 85 DEG C is 14.9mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 93.5% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 4
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 4.25g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone DTE-1 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 42.0g propylene
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acid amides, 16.25g, on the basis of the total content of monomer and distilled water,
The total content of monomer is 27 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 50mg is added
Auxiliary agent urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammoniacal liquor and 10mgN, N- methylene-bisacrylamide, while use hydroxide
Reactor is placed in water-bath to 8.0 by sodium regulation system pH value, is passed through the high pure nitrogen 30 minutes that volumetric concentration is 99.99%
To remove the oxygen in polymerisation bottle.Then 15mg ammonium persulfates, 20mg sodium hydrogensulfites are sequentially added, continues to be passed through high-purity
Nitrogen 10 minutes, adiabatic reaction 8 hours, the transparent polymer product with viscosity is obtained, through being granulated, drying, crushing, sieving
To the polymer P 4 of tool surface active function.
According to the dosage of structures alone DTE-1 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (14)
It can calculate and learn, in the polymer P 4 of tool surface active function, the content of the construction unit of derived from acrylamides is about
67.2 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 26 weight %, is derived from
The content of structures alone DTE-1 construction unit shown in formula (14) is about 6.8 weight %.
The intrinsic viscosity for having the polymer P 4 of surface active function is 2223mL/g, and viscosity average molecular weigh is 1221 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 34.8mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 29.7mPa.s, and the apparent viscosity at 85 DEG C is 15.8mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 90.3% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 5
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 3.75g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone DTE-2 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 43.75g third
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 15g, it is single on the basis of the total content of monomer and distilled water
The total content of body is 22 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 50mg is added to help
Agent urea, 150mg disodium ethylene diamine tetraacetates, 2mL ammoniacal liquor and 20mgN, N- methylene-bisacrylamide, while use sodium hydroxide
Reactor is placed in water-bath to 8.0 by regulation system pH value, be passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes with
Remove the oxygen in polymerisation bottle.Then 15mg ammonium persulfates, 30mg sodium hydrogensulfites are sequentially added, continues to be passed through High Purity Nitrogen
Gas 10 minutes, adiabatic reaction 8 hours, the transparent polymer product with viscosity is obtained, through being granulated, drying, crushing, sieving and obtain
Has the polymer P 5 of surface active function.
According to the dosage of structures alone DTE-2 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (15)
It can calculate and learn, in the polymer P 5 of tool surface active function, the content of the construction unit of derived from acrylamides is about
70 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 24 weight %, derived from formula
(15) content of the construction unit of structures alone DTE-2 shown in is about 6 weight %.
The intrinsic viscosity for having the polymer P 5 of surface active function is 2497mL/g, and viscosity average molecular weigh is 1415 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 35.1mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 33.7mPa.s, and the apparent viscosity at 85 DEG C is 17.2mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 91.7% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 6
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 3.125g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(16) structures alone DTE-3 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 43.75g third
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 15.625g, using the total content of monomer and distilled water as base
Standard, the total content of monomer is 28 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then add
50mg auxiliary agents urea, 150mg disodium ethylene diamine tetraacetates, 2mL ammoniacal liquor and 5mg dimethyl sulfoureas, while adjusted with sodium hydroxide
Reactor is placed in water-bath to 8.0 by system pH, is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove
Oxygen in polymerisation bottle.Then 15mg ammonium persulfates, 15mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10
Minute, adiabatic reaction 8 hours, the transparent polymer product with viscosity is obtained, through being granulated, drying, crushing, sieving and obtain tool table
The polymer P 6 of face active function.
According to the dosage of structures alone DTE-3 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (16)
It can calculate and learn, in the polymer P 6 of tool surface active function, the content of the construction unit of derived from acrylamides is about
70 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 25 weight %, derived from formula
(16) content of the construction unit of structures alone DTE-3 shown in is about 5 weight %.
The intrinsic viscosity for having the polymer P 6 of surface active function is 2804mL/g, and viscosity average molecular weigh is 1636 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 35.5mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 37.8mPa.s, and the apparent viscosity at 85 DEG C is 21.6mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 91.2% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 7
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 5.25g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone DTE-1 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 32.25g third
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 25g, it is single on the basis of the total content of monomer and distilled water
The total content of body is 20 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then 50mg is added to help
Agent urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammoniacal liquor and 5mg dimethyl sulfoureas, while with sodium hydroxide regulation system pH
Reactor is placed in water-bath to 8.5, is passed through the high pure nitrogen that volumetric concentration is 99.99% and is polymerize instead with removing for 30 minutes by value
Answer the oxygen in bottle.Then 15mg ammonium persulfates, 30mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes,
Adiabatic reaction 8 hours, obtain the transparent polymer product with viscosity, through be granulated, dry, crush, sieve obtain have surface live
The polymer P 7 of sexual function.
According to the dosage of structures alone DTE-1 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (14)
It can calculate and learn, in the polymer P 7 of tool surface active function, the content of the construction unit of derived from acrylamides is about
51.6 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 40 weight %, is derived from
The content of structures alone DTE-1 construction unit shown in formula (14) is about 8.4 weight %.
The intrinsic viscosity for having the polymer P 7 of surface active function is 2876mL/g, and viscosity average molecular weigh is 1688 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 33.9mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 39.5mPa.s, and the apparent viscosity at 85 DEG C is 22.8mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 92.8% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Embodiment 8
The present embodiment is used for illustrating according to polymer of tool surface active function of the present invention and preparation method thereof.
Using aqueous solution polymerization method, 6.25g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone DTE-2 shown in (Zhangjiagang Tianding Chemical Co., Ltd.) is as water-soluble surface-active monomer, 46.875g third
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 9.375g, using the total content of monomer and distilled water as base
Standard, the total content of monomer is 30 weight %, and the solution being stirred well in polymerisation bottle is changed into clear solution.Then add
50mg auxiliary agents urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammoniacal liquor and 20mg dimethyl sulfoureas, while adjusted with sodium hydroxide
Reactor is placed in water-bath to 8.5 by system pH, is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove
Oxygen in polymerisation bottle.Then 15mg ammonium persulfates, 15mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10
Minute, adiabatic reaction 8 hours, the transparent polymer product with viscosity is obtained, through being granulated, drying, crushing, sieving and obtain tool table
The polymer P 8 of face active function.
According to the dosage of structures alone DTE-2 shown in acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and formula (15)
It can calculate and learn, in the polymer P 8 of tool surface active function, the content of the construction unit of derived from acrylamides is about
75 weight %, the content of the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 15 weight %, derived from formula
(15) content of the construction unit of structures alone DTE-2 shown in is about 10 weight %.
The intrinsic viscosity for having the polymer P 8 of surface active function is 3038mL/g, and viscosity average molecular weigh is 1808 × 104, gather
When polymer solution concentration is 1500mg/L, surface tension 33.0mN/m.The simulated formation for being 10000mg/L with oil field salinity
Water prepared polymer solution, it is 1500mg/L, shear rate 7.34s in polymer solution concentration-1Under conditions of, polymer is molten
Apparent viscosity of the liquid at 25 DEG C is 43.3mPa.s, and the apparent viscosity at 85 DEG C is 25.6mPa.s, and polymer solution is 90
Apparent viscosity conservation rate is 93.1% after aging 1 month in substantially free of environment at DEG C, shows obtained tool surface-active work(
The polymer of energy has good surface-active, temperature-resistant anti-salt ability and good ageing resistace.
Comparative example 1
Comparative sample KYP (oil field offer) is contrasted with polymer P 2, polymer P 6 and polymer P 8, observes different temperatures
The apparent viscosity of lower aqueous solutions of polymers (concentration 1500mg/L, salinity 10000mg/L), as a result as shown in Figure 1.
It will be seen from figure 1 that according to polymer P 2, polymer P 6 and the polymer P 8 of the present invention at 85 DEG C still with higher
Apparent viscosity, the aqueous solution apparent viscosity of polymer P 2, P6 and P8 can reach 13.3-25.6mPa.s, and what oil field provided
Code name is that the apparent viscosity of the aqueous solution of KYP acrylamide polymer is only 8.9mPas, shows the tool table according to the present invention
The polymer of face active function has good temperature-resistant anti-salt performance.
Comparative example 2
Comparative sample KYP (oil field offer) is contrasted with polymer P 2, polymer P 6 and polymer P 8, observation salinity
Surface tension of the aqueous solutions of polymers for the various concentrations prepared for 10000mg/L simulated formation water at 30 DEG C, as a result such as
Shown in Fig. 2.
Figure it is seen that with the increase of concentration, according to the polymer P 2 of the present invention, polymer P 6 and polymer P 8
The surface tension of the aqueous solution is gradually reduced, when concentration is 1500mg/L, the aqueous solution of polymer P 2, polymer P 6 and polymer P 8
Surface tension between 33-35.5N/m, show good surface-active.The surface of the comparative sample KYP aqueous solution
Power declines with the increase of concentration, but fall very little, and surface tension is between 60-70mN/m.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of polymer for having surface active function, it is characterised in that the polymer of the tool surface active function contains structure
Unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (1), knot
Structure unit B is the construction unit with structure shown in formula (2), and construction unit C is the construction unit with structure shown in formula (3)；
Wherein, on the basis of the weight of the polymer of the tool surface active function, construction unit A content is 45-89 weight %, knot
The content of structure unit B is that 10-40 weight %, construction unit C content are 1-15 weight %, the polymer for having surface active function
Viscosity average molecular weigh be 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, R4And R5It is each independently H
Or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, R7For C1-C17Alkyl.
2. polymer according to claim 1, wherein, on the basis of the weight of the polymer, the construction unit A's
Content is that 50-75 weight %, the construction unit B content are that 15-40 weight %, construction unit C content is 5-10
Weight %, the viscosity average molecular weigh of the polymer is 6,000,000-1,850 ten thousand.
3. polymer according to claim 1, wherein, the construction unit A is the structure list with structure shown in formula (7)
Member, the construction unit B is the construction unit with structure shown in formula (8), and the construction unit C is with formula (9) institute
Show the construction unit of structure, with the construction unit of structure shown in formula (10) and with the construction unit of structure shown in formula (11)
At least one,
4. a kind of preparation method for the polymer for having surface active function, this method include：In initiator and water as solvent
In the presence of, monomer D, monomer E and monomer F is carried out solution polymerization, wherein, the monomer D is with knot formula (4) Suo Shi
The monomer of structure, the monomer E are the monomer with structure shown in formula (5), and the monomer F is the list with structure shown in formula (6)
Body, wherein, construction unit A content is in the polymer that the monomer D, monomer E and monomer F dosage to be prepared
45-89 weight %, construction unit B content are that 10-40 weight %, construction unit C content are 1-15 weight %, and are caused
The viscosity average molecular weigh for the polymer being prepared is 5,000,000-2,000 ten thousand；The construction unit A is with structure shown in formula (1)
Construction unit, the construction unit B are the construction unit with structure shown in formula (2), and the construction unit C is with formula (3)
The construction unit of shown structure,
Wherein, R1And R2It is each independently H or C1-C4Alkyl, R3For C1-C14Alkylidene, preferably methylene, R4And R5
It is each independently H or C1-C4Alkyl, and R4And R5It is asynchronously H, M H, Na or K, R6For C1-C17Alkyl, R7For C1-
C17Alkyl.
5. according to the method for claim 4, wherein, the monomer D, monomer E and monomer F dosage cause what is be prepared
Construction unit A content is that 50-75 weight %, construction unit B content are 15-40 weight % in polymer, construction unit C's
Content is 5-10 weight %, and the viscosity average molecular weigh for the polymer for be prepared is 6,000,000-1,850 ten thousand.
6. according to the method for claim 4, wherein, the monomer D is the monomer with structure shown in formula (12)；The list
Body E is the monomer with structure shown in formula (13)；The monomer F is with the monomer of structure shown in formula (14), with formula (15)
The monomer of shown structure and there is at least one of monomer of structure shown in formula (16),
7. according to the method described in any one in claim 4-6, wherein, the condition of the solution polymerization includes：
Carried out under adiabatic condition, time 2-15h, preferably 5-10h.
8. according to the method described in any one in claim 4-6, wherein, the initiator includes azo-initiator, mistake
At least one of oxide-based initiator and redox type initiators；The azo-initiator is selected from the isobutyric acid of azo two
Dimethyl ester, azo-bis-isobutyrate hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group
Formamide, azo diisopropyl imidazoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azo two
At least one of isobutyl cyanide and ABVN；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, mistake
At least one of sodium sulphate, potassium peroxydisulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester；The redox class is drawn
Send out agent in sulfate-sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine extremely
Few one kind.
9. the polymer for the tool surface active function that the method in claim 4-8 described in any one is prepared.
10. the polymer of the tool surface active function in claim 1-3 and 9 described in any one is as polymer oil-displacing agent
Using.
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|---|---|---|---|---|
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| CN104628944A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
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| JP2003041135A (en) * | 2001-07-26 | 2003-02-13 | Hymo Corp | Water-soluble polymer dispersion and method for producing the same |
| CN104628944A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
| CN104693351A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
| CN104693374A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
| CN105482034A (en) * | 2014-09-19 | 2016-04-13 | 中国石油化工股份有限公司 | Functional polymer with surface activity and preparation method for functional polymer and application of functional polymer |
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